Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
  • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
  • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

• the present invention relates to a process for preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• 2,3,3,3-Tetrafluoropropene has zero ozone depletion potential (ODP) and an extremely low global warming potential (GWP), and is thus drawing attention as a component of e.g. refrigerants and mixed refrigerants that can be used as an alternative for chlorofluorocarbon.
• ODP ozone depletion potential
• GWP extremely low global warming potential
• 2,3,3,3-tetrafluoropropene is useful not only as a propellant, heat transfer medium, or fire-extinguishing agent, but also as a monomer component in a polymer.
• this method is not practical because its yield is low due to the formation of many impurities, and improvements are thus needed, and also because the catalyst is deteriorated in a short period of time.
• this method has economic problems because the steps are complicated and long with many stages.
• US 2009/0240090 discloses a method in which HCC-240db represented by CCl 3 CHClCH 2 Cl as a starting material is reacted with HF in the gas phase at a reaction temperature of 255°C in the presence of a fluorinated Cr catalyst.
• this method is not considered to be a practical preparation method of HFO-1234yf because HFO-1234yf is produced only in an amount of 0.5% in combination with HFC-245cb, and the main product is HCFC-1233xf (98.3% production).
• HCC-1230xa is used as a starting material in this method, catalyst deterioration due to olefin polymerization advances, and both oxygen entrainment and a stabilizer, such as a polymerization inhibitor, are required in order to inhibit the deterioration. This causes an increase in the economic cost.
• a main object of the present invention is to provide a process for efficiently preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf) by a simple and economically advantageous method that is suitable for implementation on an industrial scale.
• the present inventors conducted extensive studies to achieve the above object and, as a result, surprisingly found that the desired HFO-1234yf can be prepared with a high yield through the operation of a single-step reaction by a method in which 1,1,1,2,3-pentachloropropane (HCC-240db) is used as a starting material and reacted with HF in the gas phase under heating in the presence of oxygen, in the presence of a specific chromic oxide catalyst. Further, the present inventors found that it is possible to efficiently prepare HFO-1234yf on an industrial scale by eliminating problems in conventional HFO-1234yf preparation methods, and completed the present invention.
• the term "chromic oxide catalyst” may refer to chromic oxide or fluorinated chromic oxide obtained by fluorinating chromic oxide.
• stabilizers such as polymerization inhibitors
• HCC-240db 1,1,1,2,3-pentachloropropane
• HFC-245cb a compound represented by the structural formula:
• the present invention provides a process for preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf) comprising the step of (1) reacting, in a reactor and in the gas phase in the temperature range of 320-390°C, 1,1,1,2,3-pentachloropropane (HCC-240db) with 10-100 mol HF per mole of HCC-240db, and in the presence of
• HCC-240db 1,1,1,2,3-pentachloropropane
• the desired HFO-1234yf can be prepared with a high yield by a single-step reaction process by using the above compound as a raw material to react with HF in accordance with the later-described conditions.
• HCC-240db is an advantageous starting compound in terms of easy availability and low cost.
• the preparation process of the present invention is a process in which, in a reactor , the HCC-240db is reacted with HF in the gas phase under heating in the presence of oxygen, in the presence of a specific chromic oxide catalyst.
• the process of the present invention for preparing HFO-1234yf is characterized by comprising the step of:
• the desired HFO-1234yf can be obtained with high selectivity by a single-step reaction process, by reacting the starting compound with HF under such conditions.
• the shape of the reactor used in the process of the present invention is not particularly limited.
• an adiabatic reactor packed with a catalyst a multitubular reactor in which a heating medium is used to remove heat and homogenize the temperature distribution in the reactor, and other like reactors may be used.
• HF may usually be supplied in the gas phase to a reactor together with a starting compound.
• the amount of HF supplied is in the range of 10-100 mol, preferably 15-50 mol, and more preferably 15-35 mol, per mole of the above-described HCC-240db starting compound.
• the formation of impurities can be reduced by setting the amount of HF supplied within the above range, making it possible to recover HFO-1234yf from the product with high selectivity and a high yield.
• Oxygen is usually supplied in an amount of 0.02-1 mol per mole of HCC-240db as a starting compound. Oxygen is preferably supplied in the range of 0.05-0.5 mol, and more preferably 0.05-0.4 mol, per mole of HCC-240db. The amount of oxygen supplied is set within the above range, thereby making it possible to prevent catalyst deterioration and maintain high catalytic activity. As for the form of oxygen supply, oxygen may be singly supplied, or oxygen may be diluted with an inert gas, such as nitrogen (which may be supplied as air), helium, or argon.
• an inert gas such as nitrogen (which may be supplied as air), helium, or argon.
• the reaction temperature i.e., the temperature in the reactor
• the reaction temperature is in the range of 320-390°C, and more preferably 330-380°C. These are temperature ranges in which the reaction is carried out in the gas phase.
• the temperature is higher than the above temperature ranges, the selectivity of HFO-1234yf is decreased; while when the temperature is lower than the above temperature ranges, the period during which good catalytic activity can be maintained is shortened. Therefore, neither case is preferable.
• HCl hydrogen chloride
• At least one compound (usable material) selected from HCFC-1233xf and HFC-245cb and HF are preferably recycled in the reactor used in step (1) (step (2)). By further performing this recycling operation, it is possible to prepare HFO-1234yf with a high yield.
• step (2) When the usable material is recycled (step (2)), conditions such as the amounts of the HF and oxygen supplied, the type of catalyst used, such as chromic oxide, and the reaction temperature are preferably as described in step (1).
• HFO-1234yf from at least one compound (usable material) selected from 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf) and 1,1,1,2,2-pentafluoropropane (HFC-245cb), by supplying the usable material to a different reactor.
• usable material selected from 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf) and 1,1,1,2,2-pentafluoropropane (HFC-245cb)
• the reaction can be carried out at the above-described pressure at which HCC-240db and HF can exist in the gas phase, and the reaction may be carried out at a normal, increased, or reduced pressure, preferably within the range of 0.08-0.8 Mpa.
• the contact time represented by W/Fo i.e., a ratio of the amount of packed catalyst W(g) to the total flow rate Fo (a flow rate at 0°C, 0.10133 MPa (1 atm): cm 3 /s) of the raw material gases supplied to the reactor, may be generally adjusted to a range of 2-30 g ⁇ s/cm 3 , and preferably 4-20 g ⁇ s/cm 3 .
• the reaction time (W/Fo) within the above range, it is possible to maintain a high selectivity of HFO-1234yf.
• HFO-1234yf can be prepared with a better yield by performing steps (1) and (2) in a continuous manner.
• steps (1) and (2) can be performed as a continuous operation by the following manner: (i) the reaction of step (1) is performed; (ii) HCl is separated and removed from the reactor outlet components; (iii) HFO-1234yf is then separated; and subsequently, (iv) at least one compound of HFC-245cb and HCFC-1233xf, and HF are recycled.
• HFO-1234yf obtained by separation and recovery can be recovered after HFO-1234yf is purified by distillation or the like to remove impurities formed by reaction, and may be used as- is in the intended application or converted to a different compound.
• chromic oxide catalyst an example of usable chromic oxide is represented by the composition formula CrOm, wherein m is in the range of 1.5 ⁇ m ⁇ 3, preferably 2-2.75, and more preferably 2-2.3.
• the form of chromic oxide catalyst is not limited. As long as the form is suitable for reaction, chromic oxide catalyst in any form, such as a powder or pellet, can be used, with a pellet being particularly preferable.
• the above-described chromic oxide catalyst can be prepared, for example, by the method disclosed in JP-A-H05-146680 . Further, fluorinated chromic oxide can also be prepared by the method disclosed in JP-A_H05-146680 .
• chromic oxide obtained by the above-described method is fluorinated (HF treatment) with HF, thereby obtaining fluorinated chromic oxide.
• the temperature for fluorination is, for example, 100-460°C.
• the surface area of the catalyst is decreased by fluorination treatment. Generally, the catalyst becomes more active when the specific surface area is higher.
• the specific surface area when fluorinated is preferably 25-130 m 2 /g and more preferably 40-100 m 2 /g; however, it is not limited to this range.
• the fluorination reaction of chromic oxide may be performed prior to the implementation of the process of the present invention (described later) by supplying HF to a reactor packed with chromic oxide. After chromic oxide is fluorinated by this method, the formation reaction of HFO-1234yf can be progressed by supplying HCC-240db as a raw material to the reactor.
• the degree of fluorination is not particularly limited.
• chromic oxide containing 10-30% fluorine can be suitably used.
• the present invention can also use, as a chromium oxide catalyst or fluorinated chrome oxide catalyst, the amorphous chromium-based catalyst disclosed in JP-A-H11-171806 , mainly comprising a chromium compound containing at least one metallic element selected from indium, gallium, cobalt, nickel, zinc, and aluminum, wherein chromium in the chromium compound has an average valence number of +3.5 or higher and +5.0 or less.
• the above-described fluorination catalyst comprising chromic oxide or fluorinated chromic oxide may be used as supported on a carrier, such as alumina or activated carbon.
• the present invention uses fluorination-treated chromic oxide for reaction, the use of fluorinated chromic oxide is particularly preferable.
• usable materials such as HCFC-1233xf and HFC-245cb
• the preparation process of the present invention can be performed under mild conditions, such as normal pressure, reduced pressure, and the like. It is a preparation process that utilizes the gas phase, which is suitable for continuous production.
• the desired HFO-1234yf can be obtained while maintaining the long life of a catalyst, by eliminating drawbacks of conventional production methods that use catalysts.
• the present process is industrially very useful as a process for preparing HFO-1234yf.
• Soft iron powder (9.72 g, 171 mmol), triethyl phosphate (48 g, 260 mmol), ferric chloride (200 mg), and carbon tetrachloride (810 g, 5.26 mol) were placed in an autoclave (1,000 mL) equipped with a thermometer, a vacuum line, a nitrogen purge line, a feeding line, a gauge, and a pressure-opening valve. The mixture was purged with nitrogen 5 times and with ethylene 1 time. The inside of the autoclave was evacuated and ethylene was fed until the gauge pressure was 0.4 MPa while stirring. The reaction started when the autoclave was heated to 110°C.
• the inner temperature was raised to 134°C, and the pressured was dropped from 0.8 MPa to 0.25 MPa. While maintaining the ethylene pressure at 0.8 MPa, the mixture was stirred at an inner temperature of 120°C for 9 hours. Subsequently, triethyl phosphate (24 g, 130 mmol) was injected, and the reaction was further carried out at 120°C for 7 hours.
• the crude product was analyzed by gas chromatography, and a complete consumption of carbon tetrachloride was confirmed.
• the crude product was washed twice with water in an amount three times the volume of the crude product, and the organic layer was dried on magnesium sulfate, thereby obtaining HCC-250fb having a gas chromatography purity of 79.8%.
• a by-product was an oligomer in which HCl is bound to ethylene.
• the thus-obtained crude product was distilled under reduced pressure (1.333 kPa (10 mmHg)) to collect fractions of 70 to 74°C, thereby obtaining HCC-250fb (814 g, 4.94 mol, yield of 91%) having a purity of 98% or higher.
• HCC-250fb (540 g, 3.0 mol) obtained in step (1), 40% KOH aqueous solution (630 g), and a phase transfer catalyst (Aliquat 336, 10 g) were placed in a four-necked flask (1,000 mL) equipped with a thermometer and a cooling tube. While stirring, the mixture was reacted in an oil bath at 80°C for 3 hours.
• the content was stirred while being irradiated with ultraviolet light, and chlorine gas was introduced at 20-120 ml/min from one gas inlet to the space above the liquid surface of the content.
• the reaction mixture was occasionally sampled to analyze the reaction mixture by gas chromatography analysis so as to measure the degree of chlorination.
• a catalyst (containing about 17.0% of fluorine) obtained by fluorinating chromic oxide comprising a composition of CrO 2.0 was packed in a tubular reactor made of Hastelloy having an inner diameter of 15 mm and a length of 1 m.
• insertion tubes were inserted from the top to measure the temperature in the inside of the catalytic packed-bed reactor at three points, and the average of these temperatures was regarded as the reaction temperature.
• the inside of the reactor was maintained at atmospheric pressure (1 atm) and 300°C, and 160 cm 3 /min of anhydrous HF and 100 cm 3 /min of nitrogen (N 2 ) were supplied to the reactor for 2 hours. Subsequently, the supply of nitrogen (N 2 ) was stopped, the reactor temperature was changed to 360°C, and oxygen (O 2 ) was supplied to the reactor at 2.0 cm 3 /min for an additional 1 hour. Then, HCC-240db (purity of 99.6%) was supplied at a rate of 10.0 cm 3 /min, and the reaction was started at this point. The molar ratio of HF to HCC-240db was 16, and the contact time (W/F 0 ) was 6.0 g ⁇ s/cm 3 .
• reaction products high-boiling-point products having a boiling point of 50°C or higher were quantified in the manner described below.
• HCFC-225 in which a predetermined amount of perchloroethylene was dissolved as an internal standard material was mixed with ice water to achieve liquid separation.
• Reactor outlet components were bubbled into the HCFC-225 layer for a certain period of time so as to extract organic materials from the HCFC-225 layer, and the acid content in HF and HCl was dissolved in the ice water.
• the extract was heated to 20°C, and the HCFC-225 layer was analyzed by gas chromatography (FID) using a DB-624 (60 m) capillary column as the column.
• FID gas chromatography
• the production amount of each product was converted to a molar ratio based on the ratio of the detected area of perchloroethylene as the internal standard material to the detected area of each product, by considering the coefficient of each product in gas chromatography.
• low-boiling-point products having a boiling point of 50°C or lower were quantified in the manner described below. Specifically, two washing columns that were connected in series and filled with water were coupled to the reactor outlet and immersed in a water bath to be preliminarily heated to 60°C. Subsequently, the reactor effluent was introduced into the washing columns and subjected to bubbling to wash the acid content. Then, the gas component dehydrated through a CaCl 2 tube was collected and analyzed by gas chromatography (FID). At this time, a predetermined amount of HFC-32 as the internal standard material was introduced together with the reactor effluent from the reactor outlet side to the washing columns.
• FID gas chromatography
• a GS-GasPro (60 m) capillary column was used as the column.
• the production amount of each product was converted to a molar ratio based on the ratio of the detected area of HFC-32 as the internal standard material to the detected area of each product, by considering the coefficient of each product in gas chromatography.
• CF 3 CCl CHCl (HCFC-1223xd-E form + Z form)
• CF 3 CH CHCl (HCFC-1233zd-E form + Z form)
• CF 3 CH CHF (HFC-1234ze-E form + Z form)
• CF 3 CH CH 2 (HFC-1243zf)
• a reaction was carried out under conditions similar to those of Example 1, except that the amount of packed catalyst used was changed to 39.0 g; anhydrous HF was supplied to the reactor at 224 cm 3 /min; oxygen (O 2 ) was supplied to the reactor at 0.8 cm 3 /min; HCC-240db (purity of 99.6%) was supplied to the reactor at 8.0 cm 3 /min; and the reaction temperature was changed to 355°C.
• the molar ratio of HF to HCC-240db was 28, and the contact time (W/F 0 ) was 10.1 g ⁇ s/cm 3 . Table 1 shows the results of analysis at a time point 39 hours after the start of the reaction.
• a reaction was carried out under conditions similar to those of Example 1, except that the amount of packed catalyst used was changed to 34.0 g; anhydrous HF was supplied to the reactor at 192 cm 3 /min; HCC-240db (purity 99.6%) was supplied to the reactor at 8.0 cm 3 /min; and the reaction temperature was changed to 345°C.
• the molar ratio of HF to HCC-240db was 24, and the contact time (W/F 0 ) was 10.1 g ⁇ s/cm 3 .
• Table 1 shows the results of analysis at a time point 28 hours after the start of the reaction.
• a reaction was carried out under conditions similar to those of Example 1, except that oxygen (O 2 ) was supplied to the reactor at 4.0 cm 3 /min (and the reaction temperature was changed to 305°C.
• the molar ratio of HF to HCC-240db was 16, and the contact time (W/F 0 ) was 5.9 g ⁇ s/cm 3 .
• Table 2 shows the results obtained 166 hours after the start of the reaction as Comparative Example 1.
• Example 2 A reaction was carried out under conditions similar to those of Example 1, except that the temperature was changed to 405°C.
• the molar ratio of HF to HCC-240db was 16, and the contact time (W/F 0 ) was 6.0 g ⁇ s/cm 3 .
• Table 2 shows the results obtained 12 hours after the start of the reaction as Comparative Example 2.
• Example 2 A reaction was carried out under conditions similar to those of Example 1, except that no oxygen (O 2 ) was supplied to the reactor and the temperature was changed to 355°C.
• the molar ratio of HF to HCC-240db was 16, and the contact time (W/F 0 ) was 6.1 g ⁇ s/cm 3 .
• Table 2 shows the results obtained 24 and 190 hours after the start of the reaction as Comparative Examples 3-1 and 3-2, respectively.
• a reaction was carried out under conditions similar to those of Example 1, except that the amount of packed catalyst used was changed to 15.2 g; anhydrous HF was supplied to the reactor at 80 cm 3 /min; oxygen (O 2 ) was supplied to the reactor at 1.0 cm 3 /min; and the reaction temperature was changed to 355°C.
• the molar ratio of HF to HCC-240db was 8, and the contact time (W/F 0 ) was 10.0 g ⁇ s/cm 3 .
• Table 2 shows the results at a time point 16 hours after the start of the reaction as Comparative Example 4.
• Molar ratio (HF/240db) indicates the molar ratio of HF to HCC-240db.
• the table shows that 16 mol of HF is supplied per mole of HCC-240db in Example 1-1.
• O 2 /240db (mol%) indicates the ratio of O 2 to HCC-240db in mol%.
• the table shows that 20 mol of O 2 is supplied relative to 100 mol of HCC-240db (in other words, 0.2 mol of O 2 is supplied per mole of HCC-240db) in Example 1-1.
• HFC-245cd should read HFC-245cb.
• Example 1-1 Example 1-2
• Example 2 Example 3 Reaction temperature (°C) 360 360 355 345 Molar ratio (HF/240db) 16 16 28 24 W/F 0 (g ⁇ s/cm 3 ) 6.0 6.0 10.1 10.1 O 2 /240db (mol%) 20 20 10 25 Time (h) after the start of the reaction 22 165 39 28 Conversion (%) of raw material 100 100 100 100 Selectivity (%) of useful materials HFO-1234yf 13.6 13.7 16.3 12.5 HCFC-1233xf 79.9 79.6 77.2 82.6 HFC-245cd 2.4 2.5 4.3 3.4 Selectivity (%) of impurities HCFC-1223xd 2.1 2.1 1.0 0.7 HCFC-1233zd 0.3 0.3 0.2 0.1 HFO-1234ze 0.2 0.2 0.1 0.1 HFC-245fa 0.1 0.1 0.1 0 HFC-1243zf 0.2 0.2 0.1 0.1 Others 1.2 1.3 0.7 0.5
• HFO-1234yf was obtained using HCC-240db as a starting material by a method in which HCC-240db is reacted with a specific amount of HF under heating in the presence of a specific amount of oxygen relative to HCC-240db, in the presence of a specific chromic oxide catalyst.
• HFO-1234yf was prepared with high selectivity and a high yield.

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